Optical Absorption Spectroscopy Research Articles

Vertical Characteristics of HCHO and NO2 in Suburban Shanghai: Understanding of Ozone formation sensitivity via Secondary HCHO

Abstract Since ozone (O3) pollution in China is on the rise, vertical distribution of nitrogen dioxide (NO2) and formaldehyde (HCHO) and their role towards O3 formation are critical towards designing O3 control strategies. Seasonal characteristics of aerosols, HCHO and NO2 were investigated over suburban Shanghai using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) from June 2020 to May 2021. For HCHO, the highest average vertical mixing ratios (VMRs) were observed for summer (0.775 ppb), followed by autumn (0.719 ppb), spring (0.718 ppb) and winter (0.672 ppb) at ground level. Seasonal trends in NO2 VMRs were observed to be opposite to that of HCHO with peak values occurring during winter (2.212 ppb) at the ground level followed by autumn (1.881 ppb), spring (1.415 ppb) and summer (1.124 ppb). In vertical, aerosols depicted a Gaussian shape with a higher values between 0.2 - 0.5 km. An exponential decay in NO2 VMRs is observed from 0.0 km to 3.0 km while the integral component of HCHO was found to be concentrated up to 2.0 km particularly during summer months. The vertical distribution of NO2 in different seasons mainly appeared below 0.5 km, while that of HCHO appeared within the range of 0.2-1.0 km. Both aerosols and NO2 tend to be higher during haze days compared to non-haze days while HCHO was found to be higher during clear days owing to high photochemical activity on a clear day. Based on the ratio of HCHO to NO2 (RFN), this study attempted to quantify the vertical characteristics of O3 sensitivity for different seasons. The results indicated that the O3 sensitivity was VOC-limited both at lower (generally, 0.0 - 0.6 km) and higher heights (1.8 - 3.0 km) while some transition limited scenarios were found at middle height (0.7 – 1.7 km) particularly during daytime. The results depicted that secondary HCHO is a crucial factor controlling on O3 sensitivity over Shanghai where enhanced ratio of VOC limited regime was observed with secondary HCHO for all the seasons.

Preparation, characterization and cooling performance of ZnO based Nanofluids

Nanoparticles (NPs) of Zinc Oxide (ZnO) were synthesized by the sol–gel method. These NPs were characterized for structural vibrational, morphological, optical, and electrical properties by X-ray diffraction (XRD), Fourier Transform infrared (FT-IR) spectroscopy, Scanning Electron Microscopy (SEM), UV–Visible optical absorption spectroscopy, and dielectric spectroscopy. Structural analysis confirms that all the NPs have a single-phase rutile tetragonal structure. Also from the Scherer formula, the average particle size for this compound was found to be around 10.25 nm. From SEM images, the observed NPs are spherical in shape, with an average size ranging from 10 to 100 nm. FT-IR data indicates a Zn–O vibrational bond and confirms the ZnO structure. Further, according to the optical data analysis, these NPs show an optical band gap of around 3.27 eV and follow an indirect transition. The dielectric constant (εr) and loss constant (ε) show good dispersion with the applied frequency. Also using these NPs, a nanofluid in transformer oil (mineral oil) was prepared. Further εr & εi shows good variation with the contents of NPs in the mineral oil. This nanofluid was tested for the cooling of transformers and shows some encouraging results. Based on these results, this material seems like a good candidate for transformer insulation and cooling applications.

Doping‐Induced Performance Improvement in ReS2 Field Effect Transistors: Exploring a Heterostructure with In2O3 Quantum Dots

AbstractRhenium disulfide (ReS2) is a type of transition metal dichalcogenides (TMDs) that has potential electronic and photoelectrical applications. However, limited research has been conducted on improving its electrical properties and understanding the effect of doping on ReS2‐based devices. In this study, the enhanced electrical and photoelectrical performance of a 2D/0D heterostructure constructed by decorating the In2O3 quantum dots (QDs) on a multilayer ReS2 field‐effect transistor (FET) is reported. The In2O3 QDs are characterized by using a transmission electron microscope, optical absorption, and photoluminescence spectroscopy. The n‐doping effects with improved mobility are clearly observed, which is attributed to the electron transfer induced by the relatively high conduction band level of In2O3 QDs. Owing to the channel migration of ReS2 and traps at the ReS2/In2O3 QDs interface, additional performance improvements are observed, including reduced contact resistance, improved subthreshold swing, and increased photoresponsivity; however, the photoresponse speed is decreased. In summary, the findings suggest a novel mixed‐dimensional heterostructure for enhancing the performance of ReS2 transistors and provide insights into doping‐induced channel migration for 2D materials.

Vertical Evolution of Ozone Formation Sensitivity Based on Synchronous Vertical Observations of Ozone and Proxies for Its Precursors: Implications for Ozone Pollution Prevention Strategies.

Photochemical ozone (O3) formation in the atmospheric boundary layer occurs at both the surface and elevated altitudes. Therefore, the O3 formation sensitivity is needed to be evaluated at different altitudes before formulating an effective O3 pollution prevention and control strategy. Herein, we explore the vertical evolution of O3 formation sensitivity via synchronous observations of the vertical profiles of O3 and proxies for its precursors, formaldehyde (HCHO) and nitrogen dioxide (NO2), using multi-axis differential optical absorption spectroscopy (MAX-DOAS) in urban areas of the Beijing-Tianjin-Hebei (BTH), Yangtze River Delta (YRD), and Pearl River Delta (PRD) regions in China. The sensitivity thresholds indicated by the HCHO/NO2 ratio (FNR) varied with altitude. The VOC-limited regime dominated at the ground level, whereas the contribution of the NOx-limited regime increased with altitude, particularly on heavily polluted days. The NOx-limited and transition regimes played more important roles throughout the entire boundary layer than at the surface. The feasibility of extreme NOx reduction to mitigate the extent of the O3 pollution was evaluated using the FNR-O3 curve. Based on the surface sensitivity, the critical NOx reduction percentage for the transition from a VOC-limited to a NOx-limited regime is 45-72%, which will decrease to 27-61% when vertical evolution is considered. With the combined effects of clean air action and carbon neutrality, O3 pollution in the YRD and PRD regions will transition to the NOx-limited regime before 2030 and be mitigated with further NOx reduction.

Ultrasensitive Online NO Sensor Based on a Distributed Parallel Self-Regulating Neural Network and Ultraviolet Differential Optical Absorption Spectroscopy for Exhaled Breath Diagnosis.

The concentration of fractional exhaled nitric oxide (FeNO) is closely related to human respiratory inflammation, and the detection of its concentration plays a key role in aiding diagnosing inflammatory airway diseases. In this paper, we report a gas sensor system based on a distributed parallel self-regulating neural network (DPSRNN) model combined with ultraviolet differential optical absorption spectroscopy for detecting ppb-level FeNO concentrations. The noise signals in the spectrum are eliminated by discrete wavelet transform. The DPSRNN model is then built based on the separated multipeak characteristic absorption structure of the UV absorption spectrum of NO. Furthermore, a distributed parallel network structure is built based on each absorption feature region, which is given self-regulating weights and finally trained by a unified model structure. The final self-regulating weights obtained by the model indicate that each absorption feature region contributes a different weight to the concentration prediction. Compared with the regular convolutional neural network model structure, the proposed model has better performance by considering the effect of separated characteristic absorptions in the spectrum on the concentration and breaking the habit of bringing the spectrum as a whole into the model training in previous related studies. Lab-based results show that the sensor system can stably achieve high-precision detection of NO (2.59-750.66 ppb) with a mean absolute error of 0.17 ppb and a measurement accuracy of 0.84%, which is the best result to date. More interestingly, the proposed sensor system is capable of achieving high-precision online detection of FeNO, as confirmed by the exhaled breath analysis.

Exploring Urban XCO2 Patterns Using PRISMA Satellite: A Case Study in Shanghai

As global warming intensifies, monitoring carbon dioxide (CO2) has increasingly become a focal point of research. Investigating urban XCO2 emission systems holds paramount importance, given the pivotal role of cities as major contributors to carbon emissions. Consequently, this study centers on urban locales, employing Shanghai as a case study for a comprehensive evaluation of regional XCO2 levels. We utilized high spatial resolution imagery from the PRecursore IperSpettrale della Missione Applicativa (PRISMA) satellite to conduct an XCO2 assessment over the Baoshan District with a 30 m spatial resolution from April 2021 to October 2022. Our XCO2 analysis was conducted in two steps. Firstly, we conducted a sensitivity analysis on key parameters in the inversion process, where cloud cover severely interfered with inversion accuracy. Therefore, we developed the Fmask 4.0 cloud removal and iterative maximum a posteriori differential optical absorption spectroscopy (FIMAP-DOAS) algorithm. This novel integration eliminated cloud interference during the inversion process, achieving high-precision CO2 detection in the region. Secondly, we compared the XCO2 of the region with Level-2 data from carbon monitoring satellites such as OCO-2. The comparison results showed a strong consistency, with a root mean squared error (RMSE) of 0.75 ppm for Shanghai XCO2 data obtained from the PRISMA satellite compared to OCO-2 Level-2 data and an RMSE of 1.49 ppm compared to OCO-3. This study successfully established a high-accuracy and high-spatial-resolution XCO2 satellite monitoring system for the Shanghai area. The efficacy of the FIMAP-DOAS algorithm has been demonstrated in CO2 monitoring and inversion within urban environments, with potential applicability to other cities.

TiO2-ZnO Composite thin films fabricated by Sol-Gel spin coating for room temperature impedometric acetone sensing

Metal oxide semiconductor based volatile organic compounds (VOCs) sensors lack room temperature operation and have a poor limit of detection. In this work, TiO2-ZnO composite thin film based acetone sensors with room temperature (29 ± 2 °C) operation and good sensor response have been fabricated by sol-gel based spin coating. The thin films based on the single-phase TiO2 and ZnO together with their composites have been evaluated for their structural and surface morphological properties through X-ray diffraction and field emission scanning electron microscopy respectively. The surface chemical state of the thin films surface has been analyzed through the X-ray photoelectron spectroscopy. The optical properties of the single-phase as well as the composite phase thin films were studied by optical absorption spectroscopy. The acetone sensing characteristics of these thin films based sensors were evaluated through impedance spectroscopy. The composite thin films were found to exhibit the maximum sensor response of 93.83% with a detection threshold of 3 ppm for acetone.

Identification of O3 Sensitivity to Secondary HCHO and NO2 Measured by MAX-DOAS in Four Cities in China

This study analyzed the differences in ozone (O3) sensitivity in four different urban areas in China from February 2019 to January 2020 based on data on various near-surface pollutants from passive multi-axis differential optical absorption spectroscopy (MAX-DOAS) sites and nearby China National Environmental Monitoring Center (CNEMC) sites. Across the four cities, the nitrogen dioxide (NO2) and formaldehyde (HCHO) concentrations varied seasonally. Xianghe consistently displayed the lowest NO2 levels, suggesting reduced emissions compared to other cities. Guangzhou, a city with a robust economy and a high level of vehicle ownership, exhibited higher concentrations in spring. Summer brought elevated HCHO levels in Guangzhou, Xianghe, and Shenyang due to intensified photochemical processes. Autumn and winter showed higher HCHO concentrations in Guangzhou and Xianghe compared to Lanzhou and Shenyang. Overall, Guangzhou recorded the highest annual averages, due to its developed economy, while Xianghe’s lower NO2 levels were offset by the elevated HCHO due to higher O3 values. The analysis delved into primary and secondary HCHO sources across seasons and used carbon monoxide (CO) and O3 data. Xianghe showcased the dominance of secondary sources in summer and autumn, while Lanzhou was characterized by primary dominance throughout the year. Shenyang mirrored Xianghe’s evolution due to industrial emissions. In Guangzhou, due to the high levels of vehicular traffic and sunlight conditions, secondary sources predominantly influenced HCHO concentrations. These findings highlight the interplay between primary and secondary emissions in diverse urban settings. This study explored O3 sensitivity variations across seasons. Xianghe exhibited a balanced distribution among volatile organic compound (VOC)-limited conditions, nitrogen oxide (NOx)-limited conditions, and transitional influences. Lanzhou was mainly affected by VOC-limited conditions in winter and NOx-limited conditions in other seasons. Shenyang’s sensitivity varied with the seasons and was primarily influenced by transitions between VOCs and NOx in autumn and NOx-limited conditions otherwise. Guangzhou experienced varied influences. During periods of high O3 pollution, all regions were affected by NOx-limited conditions, indicating the necessity of NOx monitoring in these areas, especially during summer in all regions and during autumn in Xianghe and Guangzhou.

The global volcano monitoring infrastructure database (GVMID)

Monitoring volcanoes is of the most importance in volcano risk mitigation to safeguard lives and economies. Thanks to recent technological advances, both on-ground and in space, our understanding of volcanic processes has improved significantly. Though there is no one-system-fits-all, optimizing infrastructure for efficient monitoring stands as key objective. The impacts of volcanic hazards can span from local to global scales, affecting us both in the short and long term. This highlights the worldwide significance of improving volcano monitoring. Previously reliant on local ground-based instruments, today’s monitoring approach is enhanced by remote and space-based techniques such as satellite remote sensing, scanning-Differential Optical Absorption Spectroscopy (DOAS), and infrasound. Designing an effective monitoring infrastructure for volcano observatories involves careful consideration of various factors such as network coverage, type of sensors, data transmission, and power supply to ensure that the targeted parameters meet the specific needs of each volcano (e.g., type of activities, early warning systems). Additionally, fostering collaboration and information sharing within the global scientific community is essential for addressing the current challenges in volcanology. In line with this, we’ve established the Global Volcano Monitoring Infrastructure Database (GVMID) to compile data from volcano monitoring across the globe. Global Volcano Monitoring Infrastructure Database serves as an integral component of WOVOdat, the global volcano unrest database, aiming to enhance our understanding of eruptive processes and improve eruption forecasts. The database incorporates monitoring metadata comprising networks, stations, and instruments, all standardized and managed using a MySQL relational database management system. Accessed through a web-based interface (https://wovodat.org/gvmid/home.php), GVMID offers an informative snapshot and foundational overview of the techniques and instruments in place at diverse volcanoes. This interactive platform allows for queries, visualizations, and downloads, serving as a valuable resource for the volcano community. GVMID can assist observatories in various ways, by: (a) Facilitating the setup or enhancement of monitoring systems for specific volcanoes. (b) Providing insights into the latest monitoring technologies and instrumentation. (c) Identifying existing monitoring gaps that could be addressed through remote sensing infrastructure and future instrument deployments. We extend an invitation to the global volcano community to actively participate in the development and enrichment of GVMID. Our aim is for it to become a continually updated and indispensable resource that caters to diverse needs within the volcanology community.

Optical properties and electric modulus studies of TSP: CH3COONa based biopolymer electrolytes

The research of biopolymers for the creation of solid polymer electrolytes (SPE) for electrochemical devices has resulted from the green revolution. Various strategies have been used to build and characterise biopolymer-based membranes for proton and lithium-ion conduction. However, research on biopolymers based on sodium ions is uncommon in the literature. The solution cast approach is used in this work to create a SPE based on the biopolymer Tamarind Seed Polysaccharide (TSP) incorporated with sodium acetate (CH3COONa). UV–visible optical absorption spectroscopy in the wavelength range of 200–800 nm was used to investigate the optical characteristics. From the studies of optical absorption, optical transmission, optical absorption coefficient, refractive index spectrum, extinction coefficient spectra, direct energy bandgap, indirect energy bandgap, optical absorption edge, Urbach – energy, and optical dielectric loss were calculated. The comparative study of the optical dielectric loss to the optical bandgap showed that the direct allowed transition was the most probable electronic transition for the prepared films. The calculated optical bandgap (Direct allowed) was decreased for 80:20 film from 5.51 eV (for pure TSP) to 4.88 eV. The direct, indirect, and absorption edges for pure TSP were all high, and when the salt concentration of CH3COONa increased, the above characteristics progressively decreased. For 80 % TSP: 20 % CH3COONa concentration, a low direct and indirect energy bandgap value was obtained. Tangent loss and electric modulus experiment results were then presented using AC Impedance data. For the 80:20 film, the tangent energy loss revealed a minimum and the electric modulus spectra exhibited the zeroth tail is at its maximum.

CW or Pulsed laser – That is the Question: Comparative Steady‐state Photocrystallographic Analysis of Metal Nitrosyl Linkage Isomers

AbstractThe investigation of photo‐induced effects is profoundly influenced by the characteristics of photo‐excitation sources. In this study, we present a comprehensive analysis of the structures of two photoinduced linkage isomers (PLI) in a ruthenium nitrosyl complex, trans‐[Ru(py)4F(NO)](ClO4)2, following irradiation with both pulsed and continuous wave (CW) light sources under low temperature conditions. The X‐ray (photo)diffraction analysis shows that the resulting PLI generated from the two types of irradiation sources, an isonitrosyl configuration of the nitrosyl ligand in the so‐called metastable state MS1, and a side‐on configuration of the nitrosyl ligand in the metastable state MS2, are identical. In‐situ optical absorption spectroscopy was employed during CW and pulsed irradiation, enabling the monitoring of the population process of these PLI. The results obtained from the infrared spectroscopic analysis after pulsed irradiation give insight into the population mechanism illustrating that the generation of the isonitrosyl MS1 occurs through a two‐step process, via the second PLI, the side‐on configuration MS2.

Structure evolution and energy band modulation in Ba-doped BiFeO3 thin films

Bi1−xBaxFeO3 (BBFO, x = 0, 0.03, 0.1) thin films were epitaxially grown on SrRuO3-buffered SrTiO3 (001) substrates by pulsed laser deposition. With increasing Ba content, the BBFO thin films show significantly reduced leakage currents but suppressed ferroelectric polarization. X-ray diffraction reciprocal space mappings and Raman spectra indicate a structural evolution from a rhombohedral-like to tetragonal-like phase in the BBFO thin films. Optical absorption and photoelectron spectroscopy measurements demonstrate a modulation of energy band structures in the BBFO thin films. With A-site Ba acceptor doping, the BBFO thin films exhibit a blue-shift of optical bandgap and an increase in work function. The energy positions of conduction and valence bands of the BBFO thin films have been modulated, and the Fermi level shifts down to the center of the forbidden band, but acceptor-doped BFO thin films still show n-type conduction. The presence of extra oxygen vacancies by acceptor doping is supposed to make contribution to conduction behavior. This study provides a method to manipulate the functional properties and gives insights into the physics of Ba doping in BFO thin films.

Observational relationships between ammonia, carbon dioxide and water vapor under a wide range of meteorological and turbulent conditions: RITA-2021 campaign

Abstract. We present a comprehensive observational approach that aims to establish relationships between the surface–atmosphere exchange of ammonia (NH3) and CO2 uptake and transpiration by vegetation. In doing so, we study relationships useful for the improvement and development of NH3 flux representations in models. The NH3 concentration and flux are measured using a novel open-path miniDOAS (differential optical absorption spectroscopy) measurement setup, taken during the 5-week Ruisdael Land–Atmosphere Interactions Intensive Trace-gas and Aerosol measurement (RITA-2021) campaign (25 August until 12 October 2021) at the Ruisdael Observatory in Cabauw, the Netherlands. After filtering for unobstructed flow, sufficient turbulent mixing and CO2 uptake, we find the diurnal variability in the NH3 flux to be characterized by daytime emissions (0.05 µgm-2s-1 on average) and deposition at sunrise and sunset (−0.05 µgm-2s-1 on average). We first compare the NH3 flux to the observed gross primary production (GPP), representing CO2 uptake, and latent heat flux (LvE), representing net evaporation. Next, we study the observations following the main drivers of the dynamic vegetation response, which are photosynthetically active radiation (PAR), temperature (T) and the water vapor pressure deficit (VPD). Our findings indicate the dominance of the stomatal emission of NH3, with a high correlation between the observed emissions and both LvE (0.70) and PAR (0.72), as well as close similarities in the diurnal variability in the NH3 flux and GPP. However, efforts to establish relationships are hampered by the high diversity in the NH3 sources of the active agricultural region and the low data availability after filtering. Our findings show the need to collocate meteorological, carbon and nitrogen studies to advance our understanding of NH3 surface exchange and its representation.

β -rays induced displacement damage on epitaxial 4H-SiC revealed by exciton recombination

One of the most interesting wide-bandgap semiconductor is 4H-SiC that has an indirect wide-bandgap of 3.3 eV. This material holds great potential to develop power devices that find applications in the field of high-voltage and high-temperature electronics and harsh environments. In this study, we employed complementary noninvasive characterization techniques, including micro-Raman, optical absorption, steady-state, and time-resolved photoluminescence spectroscopy, to investigate the characteristics of a 12 μm thick epitaxial layer of 4H-SiC grown on 4H-SiC. Furthermore, we explored the impact of ionizing radiation on this material, utilizing β-rays and two x-ray sources. The doses are in the range of 1–100 kGy for electrons with energy of 2.5 MeV, 16 kGy for the first x-ray source (an x-ray tube with a W target operating at an anode bias voltage of 28 kV), and 100 kGy for the second x-ray source (an x-ray tube with a W target operating at an anode bias voltage of 100 kV). When exposed to the electron beam, the excitonic band at 3.2 eV exhibits a reduction in its lifetime as the deposited dose increases. In particular, in samples characterized by a greater amount of native defects, both extended and point defects, this effect becomes evident at lower deposited doses. Conversely, in the samples subjected to x-ray irradiation, these effects are not observed. These findings indicate that electron beam irradiation triggers the formation of defects associated with atomic displacement. Ultimately, we have examined the impact of thermal treatments in air, ranging from 100 to 900 °C, to investigate the recovery characteristics of 4H-SiC.

Remote Sensing Measurements at a Rural Site in China: Implications for Satellite NO2 and HCHO Measurement Uncertainty and Emissions From Fires

AbstractNitrogen dioxide (NO2) and formaldehyde (HCHO) play vital roles in atmospheric photochemical processes. Their tropospheric vertical column density (TVCD) distributions have been monitored by satellite instruments. Evaluation of these observations is essential for applying these observations to study photochemistry. Assessing satellite products using observations at rural sites, where local emissions are minimal, is particularly useful due in part to the spatial homogeneity of trace gases. In this study, we evaluate OMI and TROPOMI NO2 and HCHO TVCDs using multi‐axis differential optical absorption spectroscopy (MAX‐DOAS) measurements at a rural site in the east coast of the Shandong province, China in spring 2018 during the Ozone Photochemistry and Export from China Experiment (OPECE) measurement campaign. On days not affected by local burning, we found generally good agreement of NO2 data after using consistent a priori profiles in satellite and MAX‐DOAS retrievals and accounting for low biases in scattering weights in one of the OMI products. In comparison, satellite HCHO products exhibited weaker correlations with MAX‐DOAS data, in contrast to satellite NO2 products. However, TROPOMI HCHO products showed significantly better agreement with MAX‐DOAS measurements compared to OMI data. Furthermore, case studies of the vertical profiles measured by MAX‐DOAS on burning days revealed large enhancements of nitrous acid (HONO), NO2, and HCHO in the upper boundary layer, accompanied with considerable variability, particularly in HONO enhancements.

Absolute radiance calibration in the UV and visible spectral range using atmospheric observations during twilight

Abstract. We present an improved radiance calibration method for UV–Vis spectroscopic instruments with a narrow field of view (up to a few degrees) based on the calibration method by Wagner et al. (2015). The updated method uses only measurements during the twilight period instead of several hours as for the original method. The calibration is based on the comparison of measurements and simulations of the radiance of zenith-scattered sunlight. The main advantage of our method compared to radiance calibration methods in the laboratory is that the calibration can be directly applied in the field. This allows routine radiance calibrations whenever the sky is clear during twilight. The calibration can also be performed retrospectively and will thus be applicable for the large number of existing data sets. Also, potential changes in the instrument properties during transport from the laboratory to the field are avoided. The new version of the calibration method presented here has two main advantages. First, the required measurement period can be rather short (only a few minutes during twilight for cloud-free conditions). Second, even without knowledge of the aerosol optical depth (AOD), the errors in the calibration method are rather small, especially in the UV spectral range where they range from about 4 % at 340 nm to 8 % at 420 nm. If the AOD is known, the uncertainties are even smaller (about 3 % at 340 nm to 4 % at 420 nm). For visible wavelengths, good accuracy is only obtained if the AOD is approximately known with uncertainties from about 4 % at 420 nm to 10 % between about 550 and 700 nm (generally the AOD is nevertheless smaller in the visible than in the UV spectral range). One shortcoming of the method is that it is not possible to determine the AOD exactly at the time of the (twilight) measurements because AOD observations from sun photometer measurements or the MAX-DOAS (Multi-AXis Differential Optical Absorption Spectroscopy) measurements are usually not meaningful for such high solar zenith angle (SZA). But the related uncertainty can be minimised by repeating the radiance calibrations during the twilight periods of several days.

Nocturnal downward transport of NO3 radical from the residual layer to a surface site by the mountain breeze in Seoul, South Korea

Using the long-path differential optical absorption spectroscopy (LP-DOAS) technique, the nocturnal mixing ratios of NO3 radicals were measured at an urban site in Seoul, South Korea, from May 13 to June 12, 2022. The primary objectives of the study were to estimate the NO3 radical concentration in the nighttime boundary layer and to examine the variations in their generation and loss over time, including an evaluation of their sources and sinks. The observed mean NO3 mixing ratios and lifetimes were 16 pptv and 73 s, respectively. NO3 concentrations and lifetimes were closely associated with their production, involving O3 and NO2, as well as the loss processes regulated by NO, VOCs, and aerosol surface area. Applying the steady-state assumption for NO3 and N2O5, the mean N2O5 uptake coefficient on the aerosol surface for the entire period was 0.031. When foggy nights were excluded from the analysis, the uptake coefficient decreased to 0.025. These values are within the higher range of the results reported in other studies. High relative humidity, which averaged 75% at night throughout the collection period, favored high N2O5 uptake coefficients. NO3 concentrations generally peaked shortly after sunset and gradually declined until sunrise. However, we frequently observed distinct increases in NO3 throughout the early morning hours, especially during clear nights, when local circulation with the westerly mountain breeze prevailed at the research site. The mountain breeze transported residual air downward, resulting in 110% and 38% higher NO3 and O3 levels at the sampling locations, respectively, compared to normal conditions. This additional source of nocturnal radicals and O3 has consequences for increased secondary aerosols and O3 production, particularly at urban surface levels where they are readily depleted in the early morning hours. To this end, a more thorough examination is required to measure N2O5 and a larger spectrum of VOCs species, as these parameters are crucial for nighttime radical budgets, secondary aerosols, and O3 generation in cities like Seoul.

An all‐green cellulose acetate/corn cob composite membrane filter: A critical evaluation of its morphology and adsorption characteristics for dyes and heavy metals

AbstractIndustrial wastewater from various manufacturing sectors poses a significant environmental concern due to the release of dyes, heavy metals, and pollutants into natural water streams. Effective treatment of large volumes of industrial wastewater is crucial to mitigate this issue. Conventional industrial wastewater filtration systems often prove to be inefficient, necessitating the exploration of alternative and cost‐effective water filtration methods. In this study, we drew inspiration from the natural adsorption and purification properties of corncob to develop a novel green composite membrane filter. The composite membrane filters, named MCAPCB and MCATPCB, were formulated by incorporating powdered corncob (PCB) and alkali/hydrogen peroxide‐treated powdered corncob (TPCB) into cellulose acetate. The adsorption properties of the composite filters were evaluated using UV–Vis spectrophotometry for dye adsorption and inductively coupled plasma optical emission spectroscopy (ICP‐OES) and atomic absorption spectroscopy (AAS) for heavy metal adsorption. The results demonstrated that MCATPCB20, incorporating 20 wt% TPCB, exhibited remarkable performance in the removal of methylene blue dye, with an adsorption efficiency of 97.46%. In comparison, MCAPCB20, incorporating 20 wt% PCB, achieved a dye adsorption efficiency of 80.15%. Moreover, MCATPCB20 displayed exceptional heavy metal removal capabilities, effectively rejecting 98% and 95% of cadmium and lead, respectively, from water samples containing 1 ppm of each metal. The composite filter membranes containing 20 wt% TPCB exhibited superior adsorption efficiency, flexibility, and stability. This enhanced performance can be attributed to the higher carboxyl content in TPCB, achieved through alkali treatment, which significantly increased the adsorption capacity of MCATPCB20. Characterization studies employing XRD, SEM, contact angle, BET, ICP‐OES, and UV measurements further supported the efficacy of MCATPCB as an effective filter system for water purification.

On the influence of vertical mixing, boundary layer schemes, and temporal emission profiles on tropospheric NO2 in WRF-Chem – comparisons to in situ, satellite, and MAX-DOAS observations

Abstract. We present WRF-Chem simulations over central Europe with a spatial resolution of 3 km × 3 km and focus on nitrogen dioxide (NO2). A regional emission inventory issued by the German Environmental Agency, with a spatial resolution of 1 km × 1 km, is used as input. We demonstrate by comparison of five different model setups that significant improvements in model accuracy can be achieved by choosing the appropriate boundary layer scheme, increasing vertical mixing strength, and/or tuning the temporal modulation of the emission data (“temporal profiles”) driving the model. The model setup with improved vertical mixing is shown to produce the best results. Simulated NO2 surface concentrations are compared to measurements from a total of 275 in situ measurement stations in Germany, where the model was able to reproduce average noontime NO2 concentrations with a bias of ca. −3 % and R=0.74. The best agreement is achieved when correcting for the presumed NOy cross sensitivity of the molybdenum-based in situ measurements by computing an NOy correction factor from modelled peroxyacetyl nitrate (PAN) and nitric acid (HNO3) mixing ratios. A comparison between modelled NO2 vertical column densities (VCDs) and satellite observations from TROPOMI (TROPOspheric Monitoring Instrument) is conducted with averaging kernels taken into account. Simulations and satellite observations are shown to agree with a bias of +5.5 % and R=0.87 for monthly means. Lastly, simulated NO2 concentration profiles are compared to noontime NO2 profiles obtained from multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements at five locations in Europe. For stations within Germany, average biases of −25.3 % to +12.0 % were obtained. Outside of Germany, where lower-resolution emission data were used, biases of up to +50.7 % were observed. Overall, the study demonstrates the high sensitivity of modelled NO2 to the mixing processes in the boundary layer and the diurnal distribution of emissions.

Tropospheric bromine monoxide vertical profiles retrieved across the Alaskan Arctic in springtime

Abstract. Reactive halogen chemistry in the springtime Arctic causes ozone depletion events and alters the rate of pollution processing. There are still many uncertainties regarding this chemistry, including the multiphase recycling of halogens and how sea ice impacts the source strength of reactive bromine. Adding to these uncertainties are the impacts of a rapidly warming Arctic. We present observations from the CHACHA (CHemistry in the Arctic: Clouds, Halogens, and Aerosols) field campaign based out of Utqiaġvik, Alaska, from mid-February to mid-April of 2022 to provide information on the vertical distribution of bromine monoxide (BrO), which is a tracer for reactive bromine chemistry. Data were gathered using the Heidelberg Airborne Imaging DOAS (differential optical absorption spectroscopy) Instrument (HAIDI) on the Purdue University Airborne Laboratory for Atmospheric Research (ALAR) and employing a unique sampling technique of vertically profiling the lower atmosphere with the aircraft via “porpoising” maneuvers. Observations from HAIDI were coupled to radiative transfer model calculations to retrieve mixing ratio profiles throughout the lower atmosphere (below 1000 m), with unprecedented vertical resolution (50 m) and total information gathered (average of 17.5 degrees of freedom) for this region. A cluster analysis was used to categorize 245 retrieved BrO mixing ratio vertical profiles into four common profile shapes. We often found the highest BrO mixing ratios at the Earth's surface with a mean of nearly 30 pmol mol−1 in the lowest 50 m, indicating an important role for multiphase chemistry on the snowpack in reactive bromine production. Most lofted-BrO profiles corresponded with an aerosol profile that peaked at the same altitude (225 m above the ground), suggesting that BrO was maintained due to heterogeneous reactions on particle surfaces aloft during these profiles. A majority (11 of 15) of the identified lofted-BrO profiles occurred on a single day, 19 March 2022, over an area covering more than 24 000 km2, indicating that this was a large-scale lofted-BrO event. The clustered BrO mixing ratio profiles should be particularly useful for some MAX-DOAS (multi-axis DOAS) studies, where a priori BrO profiles and their uncertainties, used in optimal estimation inversion algorithms, are not often based on previous observations. Future MAX-DOAS studies (and past reanalyses) could rely on the profiles provided in this work to improve BrO retrievals.